Polysulfone copolymers

ABSTRACT

Copolymers consisting of 5-50% SO2, 10-90% of a monofunctional monomer such as styrene and 1-40% of a carboxylic monomer. These copolymers are water dispersible in the salt form and are useful to render cellulosic substrates water repellant, as a polish or component thereof, or as a water soluble temporary protective coating.

Moore et a1.

[ POLYSULFONE COPOLYMERS [75] Inventors: William R. Moore; Walter L.

Vaughn, both of Lake Jackson, Tex.

[73] Assignee: The Dow Chemical Company,

Midland, Mich.

[22] Filed: June 21, 1974 [21] Appl. No.: 481,623

Related US. Application Data [63] Continuation-impart of Ser. No.399,779, Sept. 21,

1973, abandoned.

[52] US. CL. 260/79.3 A; 260/29.6 T; 260/29.6 SQ [51] Int. Cl. C08113/06 [58] Field of Search 260/79.3 A

[56] References Cited UNITED STATES PATENTS 2,102,654 12/1937 Snow260/79.3 A 2,114,292 4/1938 Frey et 211... 2,198,936 4/1940 Frey et a1260/79.3 A

[ June 17, 1975 2,241,900 5/1941 Brubaker et a1. 260/79.3 A

2,253,775 8/1941 Frey et a1 260/79.3 A 2,572,185 10/1951 Noether et a1.260/79 3 A 2,703,793 3/1955 Naylor 260/79.3 A 2,778,812 l/1957 Dreisbachet a1. 260/79 3 A 3,377,324 4/1968 Mostert 260/79.3 A

FORElGN PATENTS OR APPLICATIONS 38-23041 lO/1963 Japan ..260/79.3A

Primary ExaminerRona1d W. Griffin Attorney, Agent, or Firm-Benjamin G.Colley [57] ABSTRACT Copolymers consisting of 550% 80,, lO-90% of amonofunctional monomer such as styrene and 1 4Q% of a carboxylicmonomer.

These Copolymers are water dispersible in the salt form and are usefulto render cellulosic substrates water repellant, as a polish orcomponent thereof, or as a water soluble temporary protective coating.

5 Claims, No Drawings POLYSULFONE COPOLYMERS CROSS REFERENCE TO RELATEDAPPLICATIONS This application is a continuation-in-part of Ser. No.399,779 filed Sept. 21, 1973, now abandoned.

BACKGROUND OF THE INVENTION This invention relates to a polysulfonecopolymer which is the reaction product of sulfur dioxide, amonofunctional monomer and a carboxylic monomer.

It is known from U.S. Pat. No. 3,778,812 that aa terpolymer consistingof acrylic acid, vinyl alkyl ether and sulfur dioxide can be made.Terpolymers of acrylates, propylene and sulfur dioxide are also knownfrom U.S. Pat. No. 2,703,793.

SUMMARY OF THE INVENTION It has been found that copolymers orinterpolymers generally consisting of (A) sulfur dioxide, (B) amonofunctional monomer, and (C) a carboxylic monomer can be prepared.These copolymers in the salt form are water dispersible and are usefulto render cellulosic substrates and textiles water repellant when afugitive base such as ammonia is used to prepare them. They are alsouseful as a component for polishes to obtain increased gloss, waterresistance, and ease of removal by ammonia compositions. They are alsouseful as water soluble temporary protective coatings when inorganicbases are used to prepare them.

More specifically, the copolymers of this invention consist of anessentially random polymer consisting of A. about 5 to 50 percent byweight of S B. about l0 to 90 percent by weight of a monofunctionalmonomer selected from 1. vinyl aromatic monomers having 8 to 12 carbonatoms,

2. alpha olefins of -30 carbons,

3. cycloalkylenes having 48 carbon atoms,

4. alkyl acrylates and alkyl methacrylates having 4-l2 carbon atoms,

5. vinyl alkanoates having 4-8 carbon atoms, or

6. mixtures thereof; and

C. about I to 40 percent by weight of a carboxylic monomer selected fromI. monoolefinically unsaturated dicarboxylic acids having 4-7 carbonatoms,

2. monoolefinically unsaturated monocarboxylic acids having 3-5 carbonatoms or 3. mixtures thereof.

The more preferred ranges of the monomers in the copolymers of thisinvention are about to about 30 percent by weight of (A); about 50 toabout 70 percent by weight of (B) and about 10 to about 25 percent byweight of (C).

The above copolymers are prepared in an inert organic solvent and thentreated with inorganic bases or organic bases to form the useful saltsthereof wherein the cationic moiety of the salt is an amine group, anammonium group or an alkali metal radical.

DETAILED DESCRIPTION The functional interpolymers of this invention areusually prepared by a solution precipitation process. However, othercommon polymerization techniques such as emulsion, suspension or bulkare equally effective in preparing these polymers.

In general, these functional polysulfones are prepared by saturating aninert organic solvent with sulfur dioxide gas, adding one or more of themonofunctional monomers, adding a catalyst solution and then adding thecarboxylic monomer. The addition of sulfur dioxide usually is continuedthroughout the reaction. If desired, the catalyst solution can be mixedin with the monofunctional monomers and added with them. The polymersare then neutralized with an aqueous solution of an amine, ammonia or aninorganic base.

The inert solvents that can be used for the reaction are of threegen-era] types, i.e., hydrocarbons, halogenated hydrocarbons andoxygenated hydrocarbons. Examples of the first group are benzene,n-hexane, diethylbenzene, naphtha, kerosene. Examples of the secondgroup are 1,1,l-trichloroethane, methylene chloride, perchloroethylene,chloroform, carbon tetrachloride, trichlorobenzene and the like.Examples of the third group are dioxane, methyl alcohol, butyl alcohol,acetone, methyl ethyl ketone, diethylene glycol dimethyl ether,dipropylene glycol monoethyl ether and the like. The advantage of usingthe first two groups of solvents is that the formed polymer precipitatesout and is easily processed. Use of the third group of solvents usuallyresults in a solution; the polymer is then isolated from the solvent byaqueous precipitation, distallation or evaporation or the like. Thepreferred solvents are 1,1,1-

trichloroethane, methylene chloride and acetone.

The catalysts which can be used in this process are either ionic or freeradical types. Examples of ionic types are silver nitrate, lithiumnitrate, ammonium nitrate, as well as chlorates, perchlorates, nitrites,persulfates, and the like. Examples of the second group are t-butylperoxypivalate, methyl ethyl ketone peroxide, acetyl peroxide, tertbutylperoctoate, hydrogen peroxide, azobisisobutyronitrile and the like.Ionizing radiation may also be employed. The preferred catalysts aret-butyl peroxy pivalate and ammonium nitrate. When an ionic type isemployed, the amount is generally from about 0.001 to about 0.5 percentand when the freeradical initiating type is employed, the amount isusually from about 0.05 to 5.0 percent, based on the weight ofunsaturated monomers present.

The temperature of the reaction is not critical and can range from about30C to about 50C. The preferred range is from 10 to 30C. Ceilingtemperatures of individual monomers will govern the maximum temperatureoperable. Below 30C, refrigeration costs are considerable.

The pressure used for this reaction can range from about I to pounds persquare inch (gauge) with the preferred pressure being autogenouspressure developed during the reaction conditions employed. Whenoperating outside these conditions, expensive pressure equipment isrequired.

In preparing the polysulfones of the present invention, it is generallyfound that substantially equimolar proportions of the unsaturatedmonomers and sulfur dioxide react together. In the case of styrene,tert-butyl styrene and the like, it is generally found that one mole ofsulfur dioxide reacts with two moles of these aromatic-type monomers.Starting molar ratios of sulfur dioxide to the unsaturated monomers canrange from 0.5 to l to 50:] or more to facilitate the polymerization ofthe reactants and to provide, if desired, a reaction vehicle of liquidsulfur dioxide. It is preferred to use a slight excess of S to avoid thenecessity of removing large vol umes of the gas from the polymer.

The polymers of this invention have a molecular weight range of about 1X to about 17 X 10 as determined by gel permeation chromatography intetrahydrofuran. They generally contain less than about wt. $0 in thepolymer. Differential Thermal Analysis shows no polymer transitions orreactions over a temperature range of 50-200C. Infra-red analysisconfirms a typical olefin polysulfone structure.

Examples of vinyl aromatic monomers having 8 12 carbon atoms that can beused herein are styrene, alkyl substituted styrenes, chloro substitutedstyrenes, bromo substituted styrenes, and vinyl naphthalene.

Examples of the alpha olefins of 5-30 carbon atoms that can be used arel-pentenes, l-hexenes, 1- heptenes, l-octenes, etc., as well asl-octacosenes, 1- nonacosenes and l-triacontenes. A preferred group ofalpha olefins are those having 8-18 carbon atoms. If desired, the vinylaromatic monomers can be mixed with the alpha olefins.

Examples of the cycloalkylenes having 4-8 carbon atoms are cyclopentene,cyclohexene, cyclobutene, dicyclopentadiene and the like.

Examples of the alkyl acrylates and alkyl methacrylates having 4-12carbon atoms are methyl acrylate, methyl methacrylate, ethyl acrylate,2-ethylhexy1 acrylate, butyl acrylate, butyl methacrylate and the like.

Examples of the vinyl alkanoates having 4-8 carbon atoms are vinylacetate, vinyl propionate, vinyl butyrate, vinyl pentanoate and thelike.

Examples of the monoolefinically unsaturated dicarboxylic acids having4-7 carbon atoms which can be used are maleic, fumaric, itaconic,teraconic, glutaconic, citraconic, mesaconic and vinyl succinic. It isto be understood that the corresponding anhydrides are also useful inmaking the above copolymers and that when these are neutralized thesalts of the dicarboxylic acids are formed.

Examples of the monoolefinic unsaturated monocarboxylic acids having 3-5carbon atoms that can be used are acrylic, methacrylic, crotonic,isocrotonic, angelic, and tiglic acid.

After the terpolymers are prepared in the organic solvents, theterpolymers are neutralized with either an organic base or an inorganicbase.

Examples of the organic bases that can be used are 5 monoethanalamine,methylamine, bimethylamine, ethylamine, diethylamine, trimethylamine,aminoethylethanolamine, ethylenimine, monoisopropanolamine, morpholine,ethylene diamine, pryridine, poly(ethylene glycol) diamine,tetramethylammonium hydroxide, ammonium hydroxide, and polyethylenimine.

Examples of the inorganic bases that can be used are sodium hydroxide,potassium hydroxide, lithium hydroxide, sodium carbonate, and sodiumbicarbonate.

The invention is further illustrated by the following non-limitingexamples.

EXAMPLES 1-22 Preparation of Base Polymer A 3-liter Pyrex resin kettlewas set up in a temperature-controlled glycol bath in an exhaust hood.The kettle was equipped with: a stainless steel paddle stirrer, aone-fourth inch I.D. S0 dip tube connected to a rotometer; a glassthermometer; a 5-bulb cold water condenser with drying tube. One of thesolvents listed below were charged to the reactor and then saturatedwith S0 gas by sparging for several hours at about 2 g/min. The reactorwas then charged with various monomers set forth below. The system wasagitated at 100 rpm. Catalyst was added directly to the stirred potcontents. The reaction was allowed to proceed for the desired period oftime. The polymer slowly precipitated from the reaction media. It wasthen vacuum filtered using a coarse glass-frit funnel. The polymer wassolvent-washed several times (about 1 vol. solvent per wash) and thenfiltered. The resin was then rinsed with about one liter of freshsolvent and air-dried on a filter funnel to remove most of the residualsolvent. It was then dried in a vacuum oven at about 27 inches Hg, at55C for 48 hours. The product was weighed, bottled, labeled andanalyzed. The charges, conditions, and results of a series of these runs(as generally described above) are shown in Table 1.

TABLE 1 EXAMPLE E7AMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLEStyrene, g/moles 208/20 208/20 208/20 208/20 312/30 312/30 208/20 0/0Maleic Anhydride g/moles 98/10 98/11.) 98/1.0 98/1.0 147/l.5 l47/1.549/0.5 20/0.2

M.A.)** Acr lic Acid, g/moles 0/0 0/0 0/0 0/0 0/0 0/0 0/0 0/0 Alp aOlefin, g/moles 140/1.0 0/0 0/0 0/0 0/0 253/10 1 12/05 224/10 OtherMonomer. g/moles 0/0 184/].0 0/0 132/10 0/0 0/0 0/0 O/O Solventgrams2100 2100 2100 2100 2100 2100 1560 700 Lupersol 11, grams 8.7 8.7 8.78.7 8.7 8.7 6.9 8.7 High/Low Range,

Reaction Temp. C 23/10 23/10 23/10 23/10 11/10 11/10 13/10 20/10Reaction Time, Hrs. 48 72 144 144 144 144 48 72 Product Color and Formwhite white white white white white white clear powder powder powderpowder powder powder powder visc.soln. Polymer Yield, grams 238 296 308397 290 251 402 185 Thcor. Yield, 71 olefinic monomers 42 83 55 30 81 58EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE Styrene, g/molesO/O 3l2/3.0 O/() 0/0 O/O O/O 312/30 Maleic Anhydridc. g/moles O/O 49/0.520/0.2 32/033 0/0 32/033 98/10 TABLE l-Continued EXAMPLE EXAMPLE EXAMPLEEXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE Acrylic Acid, g/moles 14/02 0/00/0 0/0 14/02 0/0 0/0 Alpha Olefin. g/moles 1 12/05' 0/0 253/10 280/10"253/10 350/25 0/0 Other Monomer. g/moles 0/0 O/O 0/0 0/0 0/0 0/0 0/0Solvent grams 500" 1000 600" 800 1000 lOOO 1000 Lupersol 11', grams 18.04.4 11.3 16.1 11.3 4.4 9.5 High/Low Range. Reaction Temp. C 23/10 28/2315/10 24/23 24/23 24/23 11/10 Reaction Time, Hrs. 216 48 44 36 36 24 36Product Color and Form hazy nonwhite white clear nonclear lt.pink whitevis.soln. powder powder visc.soln. visc.soln. semi-so1id powder PolymerYield, grams 0 394 195 126 N.A.* 302 Thcor. Yield. 71 olefinic monomers0 81 61 0 37 low 53 EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLEEXAMPLE Styrene, g/moles 104/10 312/30 208/ 0/0 0/0 208/20 312/ MaleicAnhydride'-. g/moles 25/0.25 147/1.5 49/05 49/05 0/0 98/10 O/() (22.2%(23.6% (25.3% M.A.)** M.A.)** M.A.)** Acrylic Acid. g/moles 0/0 0/0 0/00/0 49/07 0/0 72/10 (10.7% A.A.)** Alpha Olefin. g/moles 0/0 0/0 O/0506/20 506/120 196/1 .0 0/0 Other Monomer. g/molcs 32/075" ()/0 32/0250/() 0/0 0/0 O/O Solvent, grams 700 2000 800 1600" 1500" 2000 1000Lupersol 11', grams 8.7 8.7 13.1 17.3 19.9 8.7 8.7 High/Low Range,Reaction Temp.C 20/10 23/20 23/10 15/10 24/23 24/23 24/23 Reaction Time,Hrs. 24 15 24 120 1 13 48 48 Product Color and Form white white whiteyellow white white white powder powder awder oil beads powder owderPolymer Yield. grams 108 438 291 Low 276 498 14 Theor. Yield. 7:olefinic monomers 58 67 73 very low 38 72 caustic washed. 99+'/( pure.

crysta s. m.p. 52-54C.

Glacial. 200 ppm methyl ether hydroquinonc. nDccene-l. 95.671.

"Dow. inhibited l.l.l-trichlorocthanc. 954-71 pure. 767: tcrt-butylpcroxypivulute in mineral spirits. 2-Ethyl Hcxyl Acrylutc.

92+/1 pure dicyclopcntadiene.

Octudccenc-l. 92-1-71 pure.

Acetone.

Includes 3 g. DuPont \'uzo'"-azobisisobutyronitrile. 'lso m anol, 99+X'pure.

Includes 3 g. "\zizo" catalyst and 3 g. NH NO: catalyst. Butyl Acrylute.

""Fctrudeccne-l. 92+'/1 pure.

NA. not applicable.

Percent acid or anhydridc determined by titration.

EXAMPLES 23 25 Preparation of Aqueous Solutions/Dispersions of ResinsUsing N11 OH 25 of a styrene/maleic anhydride/SO terpolymer (prepared inExample 17) was dissolved in 100 g. ace- 6O tone by stirring on amagnetic stirrer overnight at room temperature to prepare a masterbatch. 25 g. portions of this master solution were placed into 2 oz.bottles and then the desired amount of 1N NH, OH was added and stirredfor about 3 hours. The results are shown in Table I1 below.

After 3 weeks of shelf stability testing at 25C. only Example 23 changedin appearance (from opaque tan color to an opaque red color). No changesin pH or viscosity were seen.

It can be seen that about one equivalent NH /eg. acid is required tocompletely solubilize the resin in the aqueous acetone solution.Excessive amounts of base pH 8) are to be avoided since polymerdegradation will slowly take place. Less than about one equivalent ofN11 will not solubilize the resin.

TABLE 11 Example Polymer Polymer Acetone 1N NH OH NH Observed Number (g)(Acid Equiv.) (g) (g) Equivalents pH Solubility 23 5 0.0227 20 30 0.03459 Soluble, clear 24 5 0.0227 20 23 0.0265 7 Soluble. clear 25 5 0.022720 20 0.0230 6 Soluble. clear EXAMPLE 26 28 Preparation of AqueousDispersions/Solutions Using Amines or NaOH 0.5 g. samples of astyrene/maleic anhydride/SO terpolymer (prepared in Example 17) wasslurried in five samples of water using a magnetic stirrer. Variousbases were added to each slurry and stirred overnight. The results areshown in Table 111 below.

Five gram portions of the master solution were diluted with g. deionizedwater to yield a 2.77% solids neutralized solution. clear andwater-white. Various plasticizers were added to make water white,solutions, stirred to make homogenous, and then mil films were cast on 8X 12 inch glass plates from these solutions. After air drying threedays, the films were observed for color, optical clarity, tack,brittleness, hardness and H 0 resistance. The results are shown in TableTABLE III Polymer Example Acid Number Equiv. Base Base g/equiv.Observations 26 0.0023 Monoethanolamine 0.373g/0.006l opaque viscouspaste 27 0.0023 NaOH 0.008/00002 slightly viscous slurry 28 0.0023 NaOH0.068/00017 viscous slurry l000 cps) A 15 mil, wet film cast from theslurry of Example 26 and ovencured at 150C for 15 minutes gave anopaque, hard, tough filmresistant to H O. When diethanolamine andtriethanolamine were tried as in Ex- IV. The films are listed indescending order of overall quality as observed.

The best plasticizers tested were the polyethylene glycol or glycerintype but all those tested decreased ample 26 the polymer precipitated.The films prepared water resistance of the cured film,

TABLE IV PLASTlClZERS Wt.% Optical Based on Clarity Hardness TotalO=Opaque S=Soft H O Ex. Name of Plasticizer Description Wt.( g) SolidsT=Transp. Tack H=Hard Resistance NONE CONTROL 0 0 T None H lnsoluble 29Diethylene Glycol Food Grade 0.50 47.5 T Heavy S Sensitive 30 Dowfax9Nl0 Ethylene oxide. Adduct of Nonyl Phenol containing 10 mole E.O./moleof phenol 0.10 15.3 T None H Very soluble 31 Dowfax 9Nl0 Ditto 0.50 47.5T None H Very soluble 32 Glycerin U.S.P. Grade 0.50 47.5 T Heavy S 81.soluble 33 Polyglycerin NC19I4 10% glycerin. 2071 diglycerin,

70% tri, tetra, penta glycerin 0.50 47.5 T None S Very soluble 34Dipropylene Glycol 0.50 52.0 T None H Very soluble Dowfax 9Nl0 0.10 35Polyglycerin NC2109 75'7( Diglycerin. 571 glycerin, 20%

tri,tetra, and penta glycerin 0.50 47.5 T Slight S S]. soluble 36Dipropylene Glycol Food Grade 0.50 47.5 Translu. Slight S Very soluble37 Polyglycol E-400 Poly(ethyleneglycol) mw=400 0.50 47.5 T Heavy S Verysoluble 38 Dipropylene Glycol Food Grade 1.00 64.4 Translu. Heavy S 51.soluble 39 Dowfax 9N40 40 moles E.O. Adduct of nonyl phenol 0.10 15.3 TNone H Very soluble 40* Dowfax 9N6 6 moles E.O. Adduct of nonyl phenol0.50 47.5 T Slight S Very soluble Example 40 had the appearance ofFisheycs.

Note: Brittlcness tests revealed all Examples (except CONTROL) to betough. CONTROL was Brittle.

from Examples '27 and 28 gave a similar film except that they were watersoluble.

EXAMPLES 29 40 Plasticized Films Cast From Aqueous Dispersions ofStyrene/Maleic Anhydride/SO NH +Salt:

A master solution of 25 g. styrene/maleic anhydride/- S0 terpolymer(prepared in Example 17) was prepared in acetone (100 g) and 123 mls. ofl N NH OH was added to this solution. Upon stirring it formed a viscousopaque dispersion (pH 7) with a styrene odor. The composition of themaster solution was:

10.10% Polymer 097% NH 48.61% H O 40.3271 Acetone EXAMPLE 41 48Crosslinked Films Cast From Aqueous Dispersions of Styrene/MaleicAnhydride/SO NH +Sa1t A master solution was prepared as in Examples3450.

Various crosslinking agents were added to 10 g. portions of the mastersolution, and then the compositions were stirred to make themhomogenous. Films (20 mils wet) were cast on 8 X 12 inch glass platesfrom these homogenous compositions. These films were oven cured at C for5 minutes. The films were then observed for color, optical clarity,brittleness, adhesion and water resistance.

It can be seen that a combination of DER 736 crosslinker and D.E.G.plasticizer gave a film with overall good properties. (See Table Vbelow).

TABLE V CROSSLINKERS Wt. "/1 Optical Brittle- Based on Clarity ness Wt.Total O=Opaque B=Brittle Ad- H O Ex. Name Description lg.) Solids ColorT=Transp. T=Tough hesion Resistance None CONTROL I 0 water T very B noneSensitive white None CONTROLJ. (D.E.G. only) 0.2 0 lt.yellow T B goodsoluble 41 D.E.R. 732 Polyglycol diglycidylether epoxide eq.wt.=305-3350.2 15.3 tan 0 very B none insensitive 42 D.E.R. 736 Polyglycoldiglycidyl ether epoxide eq.\vt. =l75-205 0.2 15.3 tan 0 very B littleinsensitive 43 Rhonite R-2 Modified urea-formaldehyde resin (Rohm &Haas) 0.2 15.3 lLbrown 0 very B fair sensitive 44 D.E.R. 732 0.2 3It.yellow 0 very B fair swellable Diethylene Glycol 0.2 (D.E.G 45 D.E.R.736 0.2 15.3 lt.yellow T B good insensitive D.E.G. 0.2 46 Rhonite R-20.2 15.3 lt.brown T B good sensitive D.E.G. 0.2 47 Dimcthyl dihydroxyethylene Urea 0.2 15.3 lt.yellow T B good soluble D.E.G. I 0.3 48$ICEPELLIICPOXKI6 7.6 lt.yellow T B good soluble EXAMPLES 49 54 In orderto illustrate the method of water-proofing 8; 3:3: mdlcates Slack Slzmgdesired for some grades cellulosic materials, samples of filter paper11.0 cm The polymers of Examples 2 and 17 were further diamter weresoaked in a 5.8% aqueous solution of the tested at 5 add on or weightpickup and 05 ammonium Salts of the P y P p in Examples on. The Examplesillustrating these results are shown in 2, 4, 8, 17, 20 and 21. TableVII below.

TABLE VII Paper With Polymer of '7! COBB INK POROSITY EXAMPLE Ex. No.Add-on TEST (I) RESISTANCE (II) (III) TYPICAL UTILITY 55 Ex. 17 5.8 22.4I800 23.4 Butcher's Wrap. Ledger Bond. Liner Paper 56 Ex. 2 5.8 24.45000 23.2 Butchcrs Wrap, Ledger Bond. Liner Paper 57 Ex. 17 0.58 113.21.1 20.4 Ruling 58 Ex. 2 0.58 115.2 3.0 18.0 Ruling CONTROL 0 109.6 0.118.2 Blotter paper, Filter Paper I- ASTM D-2045-64T II The in);resistance test was performed on a Hercules Sizing Tester using HerculesTest Ink No. 2 (Formic acid base). lll ASTM 0-72658 These samples werethen dried for 30 seconds in a hat e claim is: hot press at 370F. Thisgave a dried sample having An essemlany random copolymer conslstmg of A.about 10 to 30 ercent b wei ht of SO I It. p y g 29 about 5 8% add onweight of the po ymerlc sa B about to 70 percent y weight of Water dropswere then placed on these dried samples 1 Vin l aromatic monomers havin2 carbon and the contact angle measured. The results are shown 50 atollsg in Table VI below 2. alpha olefins having 8-18 carbon atoms,

3. cycloalkylenes having 4-8 carbon atoms,

4. alkyl acrylates or alkyl methacrylates having TABLE VI 4l2 carbonatoms, or

5. mixtures thereof; and

Paper With P lym r f Example C nta I C. about 10 to 25 ercent b wei htof monoolefini- P y g Number Angle Ti'p'cal Unmy cally unsaturateddicarboxylic acids having 4-7 carbon atoms C t I I' Il B k. "'1" m (noiid 1 16: iiiin fiisfii flg 2. A copolymer as set forth in clalm 1wherein the co- :1 gggf gl polymer 1s 1n the salt form and the cat1on1cmoiety of 17 B2 111 Ruling, winin the salt is an amine group, anammonium group or an l 3 g ii mflglllim alkali metal radical. u mg 3. Acopolymer as set forth in claim 1 wherein (B) consists of 1 and 2 4. Acopolymer as set forth in claim 1 wherein (B) consists of(l) and (3). Inthls test a i f angle greater g g 5. A copolymer as set forth in claim 1wherein (B) excellent water resistance, contact ang es 0 a out Consistsof l) and (4) UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIONPATENT NO. 3,890,287

DATED June 17, 1975 INVENTOR(S I W. R. Moore, W. L. Vaughn It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

C01. 1, lin 12, pl se correct the U.S. Pat. No. 3, 778,812

Col. 1, line 12, please correct the "aa" to a Col. 5 and 6, pleasedelete Example Nos. 1-8.

Signed and Scaled this [SEAL] A ttes t:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ufPatenlsand Trademarks

1. AN ESSENTIALLY RANDIM COPOLYMER CONSISTING OF A. ABOUT 10 TO 30PERCENT BY WEIGHT OF S02, B. ABOUT 50 TO 70 PERCENT BY WEIGHT OF 1.VINYL AROMATIC MONOMERS HAVING 8-12 CARBON ATOM
 2. ALPHA OLEFINS HAVING8-18 CARBON ATOMS,
 2. alpha olefins having 8-18 carbon atoms,
 2. Acopolymer as set forth in claim 1 wherein the copolymer is in the saltform and the cationic moiety of the salt is an amine group, an ammoniumgroup or an alkali metal radical.
 3. A copolymer as set forth in claim 1wherein (B) consists of (1) and (2).
 3. cycloalkylenes having 4-8 carbonatoms,
 3. CYCLOALKYLENES HAVING 4-8 CARBON ATOMS,
 4. ALKYL ACRYLATES ORALKYL METHACRYLATES HAVING 4-12 CARBON ATOMS, OR
 4. alkyl acrylates oralkyl methacrylates having 4-12 carbon atoms, or
 4. A copolymer as setforth in claim 1 wherein (B) consists of (1) and (3).
 5. A copolymer asset forth in claim 1 wherein (B) consists of (1) and (4).
 5. mixturesthereof; and C. about 10 to 25 percent by weight of monoolefinicallyunsaturated dicarboxylic acids having 4-7 carbon atoms.
 5. MIXTURESTHEREOF; AND C. ABOUT 10 TO 25 PERCENT BY WEIGHT OF MONOLEFINICALLYUNSATURATED DICARBOXYLIC ACIDS HAVING 4-7 CARBON ATOMS.